CN1456577A - Organic siloxane modified phenylethylene-acrylic ester nano-emulsion and preparing method thereof - Google Patents

Organic siloxane modified phenylethylene-acrylic ester nano-emulsion and preparing method thereof Download PDF

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CN1456577A
CN1456577A CN 03126653 CN03126653A CN1456577A CN 1456577 A CN1456577 A CN 1456577A CN 03126653 CN03126653 CN 03126653 CN 03126653 A CN03126653 A CN 03126653A CN 1456577 A CN1456577 A CN 1456577A
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acrylate
monomer
emulsion
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张心亚
蓝仁华
陈焕钦
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South China University of Technology SCUT
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South China University of Technology SCUT
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Abstract

An organic siloxane modifier nano-class styrene-acrylate emulsion used for paint or adhesive is prepared from the functional silane monomer with multifunctional vinylalkoxy groups and the monmers of styrene, alkyl methylacrylate, hydroxyalkyl methylacrylate, alkyl acrylate and (methyl) acrylic acid through copolymerization in the manner that under the action of organic silaxane as hydrolysis inhibitor the emulsion polymerizing is inhibited. Its advantages are low content of emulsifier, high content of solid component and storage stability (more than one year), high resistance to weather, dirt, water, chemical solvent and alkali, and high adhesion and tension strength.

Description

Organic siloxane modified vinylbenzene-acrylate nano emulsion and preparation method thereof
Technical field
The present invention relates to be used for the technical field of coatings of building external paint, water-borne wood coating, waterproof paint and metal alloy sheet material decoration coating and aqueous adhesive etc., siloxane modified vinylbenzene-acrylate nano emulsion of a kind of specifically high performance organo-silicon and preparation method thereof.
Background technology
Vinylbenzene-acrylic ester emulsion has many outstanding advantages, photostabilization, weathering resistance, resistance to acids and bases and erosion resistance as excellence, be widely used at aspects such as coating, tackiness agents, but because vinylbenzene-acrylic ester emulsion has shortcomings such as tint retention, water tolerance and tack difference.The organo-siloxane main chain is the Si-O-Si key, has the kindliness of height, and its high and low temperature resistance is good, and surface energy is low and have excellent water-resistance.
Adopt high-low temperature resistant, the low polyfunctional group organosilicon functional monomer that reaches water-tolerant of surface energy that vinylbenzene-ACRYLIC EMULSION is carried out modification, and it is made nanoemulsions, then organosilicon modified styrene-acrylate nano emulsion coating can significantly improve the hardness of filming, tensile strength, ventilation property, wear resistance, sticking power, anti-stickly put forth effort, water tolerance, chemical solvent resistance, scrub resistance, weathering resistance and contamination resistance.
At present, vinylbenzene-acrylic ester emulsion is carried out in the research of modification at polyfunctional group organosilicon function monomer, usually adopt mechanical blending or means such as grafting copolymerization process, segment copolymerization method and interact network method, as US4491650, day disclosure special permission communique [putting down] 02127458, EP297505 etc., but these methods all are solvent polymerization method basically.The emulsion copolymerization method of adopting is also arranged, as the CN1319616A[publication number], the CN1251843[publication number] etc., but that obtain all is conventional emulsions (latex particle size is greater than 100nm).
Along with requirement on environmental protection improves day by day, various countries are strict day by day to the regulation of VOC quantity discharged, and the exploitation water-borne coatings has become coating researchist's goal in research.Emulsion polymerization modified phenylethylene-acrylic ester emulsion mainly is to utilize the organosilicon function monomer contain vinyl-functional or performed polymer and vinylbenzene, acrylic ester monomer to carry out emulsion copolymerization, but both at home and abroad about organic siloxane modified vinylbenzene-acrylic ester emulsion polymeric present Research, remain in some problems from present.As owing in the letex polymerization existence of water is arranged, hydrolysis-condensation reaction can take place in the alkoxyl group in the organo-siloxane, has a strong impact on the stability in storage of polymer emulsion; Because there are huge spread in organo-siloxane and vinylbenzene, acrylate on molecular structure and polarity, can being separated etc. in various degree appear because of compatibility problem, therefore to the selection of comonomer difficulty relatively.Adopt that conventional the organic siloxane modified vinylbenzene of emulsion polymerization synthetic-acrylic ester emulsion stability is bad, the organo-siloxane addition is little, is difficult for and other monomer copolymerization.
Summary of the invention
The objective of the invention is to propose the organic siloxane modified vinylbenzene-acrylate nano emulsion of core/shell structure of a kind of synthetic easily, good stability, excellent performance.
The present invention also aims to provide the preparation method of described nanoemulsions.
Nanoemulsions is by oil, water, the thermodynamically stable transparent or semitransparent colloidal dispersion system that emulsifying agent and assistant for emulsifying agent are formed, because its emulsion particle diameter is very little, and surface tension is very low, so they have fabulous perviousness, wettability, levelling property and rheological, can infiltrate atomic thin bump maps line, in the fine capillary channel and the unusual complicated matrix surface of geometrical shape, thereby it can be used as coating, tackiness agent, goods such as soaker and printing ink are to woodenware, building stones, concrete, paper, fabric and metallic article etc. carry out high quality processing and high gloss application.Formed the filming of nanometer polymer emulsion has the fabulous transparency, can make the transparency protected varnish of material surface such as metal; Can be made into have high transparent, the polishing material of glossiness and smooth property; Can make the filler of transparent material, to improve its smoothness and glossiness; Can carry out composite use with conventional emulsions, because nanoemulsions can infiltrate space and capillary channel inside that large size emulsion particle institute can not reach, and can be filled in the space between the big emulsion particle, can significantly improve latex film strength, sticking power, smoothness and glossiness.
The nanoemulsions that the present invention proposes is the organic siloxane modified vinylbenzene-acrylate nano emulsion of a kind of core/shell structure, and it adopts the obstruction emulsion polymerization to prepare, and vinylbenzene wherein, the monomer component of acrylate are:
1) contain the alkyl acrylate of C1-C10, consumption is the 20-40% of monomer total mass;
2) contain the alkyl methacrylate of C1-C10, consumption is the 20-40% of monomer total mass;
3) contain the hydroxyalkyl methacrylate of C2-C10, consumption is the 2-10% of monomer total mass;
4) contain the thiazolinyl carboxylic acid cross-linking monomer of C3-C6, consumption is the 2-10% of monomer total mass;
5) contain the aromatics of vinyl, consumption is the 10-50% of monomer total mass.
6) contain the polyfunctional group organo-siloxane function monomer of vinyl, consumption is the 1-10% of monomer total mass.
The alkyl acrylate of described C1-C10 is one or more mixtures of methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, hexyl acrylate, Isooctyl acrylate monomer.
The alkyl methacrylate of described C1-C10 is one or more mixtures of methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, n octyl methacrylate, Isooctyl methacrylate.
The acrylic acid hydroxy alkyl ester of described C2-C10 is 2-Hydroxy ethyl acrylate, vinylformic acid-3-hydroxy propyl ester, vinylformic acid-2-hydroxyl butyl ester, vinylformic acid-5-hydroxyl pentyl ester, vinylformic acid-6-hydroxyl one or more mixtures of ester, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-2-hydroxy propyl ester.
Described C3-C6 thiazolinyl carboxylic acid cross-linking monomer is vinylformic acid or methacrylic acid and composition thereof.
Described vinyl aromatic compounds is one or more mixtures of vinylbenzene, alpha-methyl styrene, 2-chlorostyrene, 3-t-butyl styrene, 3,4-dimethyl styrene.
Described vinyl polyfunctional group organo-siloxane function monomer is one or more mixtures of vinyltrimethoxy silane, vinyl methoxyl group diethoxy silane, vinyltriethoxysilane, vinyl oxyethyl group diisopropoxy silane, vinyl silane triisopropoxide.
The present invention can adopt the semi-continuous seed emulsion polymerization method, use extraordinary emulsifying agent, adopt direct initiator or oxidation-reduction initiator, prepare the seed microemulsion earlier, again will be through pre-emulsified monomer, adopt hungry charging method in 3-5 hour, to be added drop-wise in the seed microemulsion and react, can obtain translucent organic siloxane modified vinylbenzene-acrylate nano emulsion of the present invention.
Its more specifically step comprise:
1. prepare the seed microemulsion
Water, 10-50% emulsifying agent with 20-50% joins in the reactor earlier, high-speed stirring was disperseed 10-20 minute, add aforesaid propylene acid alkyl ester, the thiazolinyl carboxylic acid of 5-20%, the vinyl aromatic compounds of 50-100% again, be warming up to 75-85 ℃, add the part initiator again, behind the stoichiometric number minute, faint blue light appears in emulsion, restir 5-20 minute, promptly form transparent seed microemulsion.
2. prepare organic siloxane modified vinylbenzene-acrylate/nano emulsion
Remaining alkyl acrylate, alkyl methacrylate, acrylic acid hydroxy alkyl ester, vinyl aromatic compounds, vinylformic acid cross-linking monomer, vinyl polyfunctional group organosilicon functional monomer, vinyl polyfunctional group organosilicon functional monomer hydrolysis inhibitor, chain-transfer agent, water and emulsifying agent etc. were stirred at a high speed 10-30 minute, make it fully emulsified, obtain monomer pre-emulsion; In 3-5 hour, be added drop-wise in the reactor continuously, react with the seed microemulsion, temperature of reaction maintains 75-85 ℃, reaction finishes, insulation 1-2 hour, cooling, the pH value of regulating microemulsion with pH value conditioning agent, filter discharging, promptly get translucent organosilicon modified styrene-acrylate/nano emulsion.
Emulsion solid content is about 45%, and particle diameter is 30-60nm.
Described chain-transfer agent can be alkyl sulfhydryl or the hydrosulphonyl silane of C5-C15, and consumption is the 1-5% of monomer total mass.
Described emulsifying agent is response type anion surfactant and nonionogenic tenside, and consumption is at below 3% of monomer total mass, and the first step consumption accounts for the 10-60% of emulsifying agent total mass.
Described initiator can be the direct initiator of persulphate, or the oxidation-reduction initiator, and consumption is below 1% of monomer total mass, and the first step consumption accounts for the 20-80% of initiator total mass.
Described pH value conditioning agent can be carbonate, supercarbonate, phosphoric acid salt, hydrophosphate or the hydrosulfate of basic metal, alkaline-earth metal or ammonium, and consumption is the 0.1-2% of monomer total amount.
The monomeric hydrolysis inhibitor of described organosilicon alcoxyl alkoxyl functional can be the di-alcohols of C2-C8, and consumption is the 0.1-2% of monomer total mass.
Organic siloxane modified vinylbenzene one acrylate nano emulsion of the core/shell structure that the present invention makes is compared with existing conventional emulsions, has the following advantages:
1. the core/shell structure nanoemulsions of the present invention's preparation had both had higher second-order transition temperature, had lower minimum film-forming temperature again, had both reduced raw materials cost, had improved the mechanical property of filming again, had increased the weathering resistance of filming.
2. the core/shell structure emulsion of the present invention's preparation is translucent nanoemulsions, and Thermodynamically stable can be stablized and store more than 1 year.
3. the core/shell structure emulsion of the present invention's preparation is translucent nanoemulsions, the emulsion particle diameter is very little, and surface tension is very low, so they have fabulous perviousness, wettability, levelling property and rheological, can infiltrate in atomic thin bump maps line, the fine capillary channel and the unusual complicated matrix surface of geometrical shape.
4. the nanoemulsions of the present invention preparation, formed filming has the fabulous transparency; Carry out composite use with conventional emulsions, can significantly improve latex film strength, sticking power, smoothness and glossiness.
5. the present invention adds acrylic or methacrylic acid cross-linking monomer in emulsion polymerization process, significantly improve the degree of crosslinking and the sticking power of latex film, need not add and after catalyzer just can make organo-siloxane and other monomer copolymerization hydrolytic crosslinking take place, reduce the consumption of emulsifying agent and initiator, increased the water tolerance of filming.
6. the present invention adds a kind of hydrolysis inhibitor of organo-siloxane in emulsion polymerization process, makes the organosilicon function monomer hydrolysis reaction can not take place before copolymerization, has increased the stability of polyreaction.
7. the present invention prepares nanoemulsions employing obstruction emulsion polymerisation process; solvent for use is a water; the emulsion of preparation is nontoxic; nonflammable; both helped environment protection; can reduce production costs again, the exterior coating ultraviolet resistance accelerated weathering test that makes with it can reach more than 3000 hours, water-proof surpasses 10000 times, can replace solvent type organic silicone modified vinylbenzene-acrylate paint for external wall fully.
Core/shell structure organosilicon-the acrylate nano emulsion of the present invention preparation than the non-silylation vinylbenzene-acrylic ester emulsion similarity condition under and silylation vinylbenzene-acrylate conventional emulsions have more superior water tolerance, scrub resistance, chemical solvent resistance, weathering resistance, contamination resistance, anti-stickly put forth effort, degree of crosslinking, sticking power, hardness and tensile strength, be widely used in top-grade building exterior coating, water-borne wood coating, waterproof paint and metal alloy sheet material decorate coating and aqueous adhesive etc.
9. nanoemulsions of the present invention, it adopts the obstruction emulsion polymerisation process to prepare.Compare with the preparation method of existing organosilicon modified styrene-acrylate, this novel polymerization process had both guaranteed the reactive behavior of unsaturated double-bond by means of chemical bond and intermolecular mechanical interlocking, the problem of phase separation that has overcome the hydrolytie polycondensation of organo-siloxane again and caused greatly owing to the polarity gap, realize the stable emulsion copolymerization of the polymkeric substance that two kinds of polarity differ greatly, and improved the package stability of polymer emulsion.The organic-silicon-modified nanoemulsions particle diameter for preparing is controlled at 30-60nm, has high performance, multifunction, and has realized the ultra micro refinement of latex particle.
Performance to the nanoemulsions of the present invention preparation can characterize with the following method: particle size of emulsion adopts Coulter LS230 particle size analyzer to measure; Being coated with film dynamic performance tests with the Instron electronic tension tester; The emulsion polymer structure is measured with Fourier infrared spectrograph (FTIR); The emulsion second-order transition temperature is measured with the trapezoidal thermometer of minimum film forming with differential scanning calorimeter (DSC), minimum film-forming temperature; The latex particle form of emulsion is measured with the micro-Electronic Speculum of scanning (TEM); The emulsion latex film is crosslinked to be measured by MEK (methyl ethyl ketone) reflux method of extraction; The pencil hardness of filming is measured by ASTM-3364; Sticking power is pressed GB/T9286-88 cross cross-hatching and is measured; The test of chemical solvent resistance (MEK) is to use by the saturated non-woven paper of MEK to come and go scouring film coated surface, the scouring number of times that record is filmed and just frayed.
Embodiment
Embodiment 1
Set of monomers becomes vinylbenzene, butyl acrylate, methyl methacrylate, methacrylic acid, hydroxyethyl methylacrylate, contains the vinyl alkoxy silane of C5-C20, and its component prescription is as table 1.
Table 1
Form mass percent, %1 vinylbenzene 252 methacrylic acids (MAA) 23 butyl acrylates (BA) 164 hydroxyethyl methylacrylates 25 vinylic organosiloxanes 16 emulsifying agents 2.57 Potassium Persulphate (K 2S 2O 8) 0.28 sodium bicarbonate, 0.19 lauryl mercaptan, 0.510 propylene glycol, 0.211 secondary deionized water, 5012 ammoniacal liquor (28%) 0.5
With 1 part of emulsifying agent, 18 parts of water, 1 part of methacrylic acid, 3 parts of butyl acrylates, 8 parts of vinylbenzene add in the reactor, stirred 20 minutes, temperature of reaction kettle is heated to 80C, drip initiator, continue to be stirred to emulsion and faint blue light occurs, after 15 minutes, begin to drip good monomer of pre-emulsification (the water high-speed stirring emulsification of remaining monomer and 30 parts 25 minutes) and initiator, in 4 hours pre-emulsion and initiator are all dripped, continue insulation 1.5 hours, cooling adds ammoniacal liquor and regulates the pH value to 7.5-8.5, the cold filtration discharging promptly gets translucent nanoemulsions of the present invention.
Embodiment 2
Set of monomers becomes butyl acrylate, vinylbenzene, vinylformic acid, Rocryl 410, contains the vinyl alkoxy silane of C5-C20, and its component prescription is as table 2.
Table 2
Form mass percent, %1 vinylbenzene (St) 252 vinylformic acid (AA) 13 butyl acrylates (BA) 154 Rocryl 410s 25 vinylic organosiloxanes 36 emulsifying agents 2.57 Potassium Persulphate (K 2S 2O 8) 0.28 sodium bicarbonate, 0.19 lauryl mercaptan, 110 ethylene glycol, 0.211 secondary deionized water 50
With 1 part of emulsifying agent, 20 parts of water, 1 part of vinylformic acid, 2 parts of butyl acrylates, 8 parts of vinylbenzene add in the reactor, stirred 20 minutes, temperature of reaction kettle is heated to 80 ℃, drip initiator, continue to be stirred to emulsion and faint blue light occurs, after 15 minutes, begin to drip good monomer of pre-emulsification (the water high-speed stirring emulsification of remaining monomer and 30 parts 25 minutes) and initiator, in 3 hours pre-emulsion and initiator are all dripped, continue insulation 2 hours, add pH value conditioning agent and regulate the pH value to 7-8, cold filtration promptly gets translucent core/shell structure organosilicon modified styrene-acrylate nano emulsion.
Embodiment 3
Set of monomers becomes vinylbenzene, Isooctyl acrylate monomer, methacrylic acid, hydroxyethyl methylacrylate, contains the vinyl alkoxy silane of C5-C20, and its component prescription is as table 3
Table 3
Form mass percent, %1 vinylbenzene 242 methacrylic acids (MAA) 13 Isooctyl acrylate monomers 164 hydroxyethyl methylacrylates 15 vinylic organosiloxanes 3.56 emulsifying agents 1.37 Potassium Persulphate (K 2S 2O 8) 0.28 sodium bicarbonate, 0.59 mercaptoethanol, 0.310 propylene glycol, 0.211 secondary deionized water 52
With 1 part of emulsifying agent, 15 parts of water, 1 part of methacrylic acid, 1 part of Isooctyl acrylate monomer, 6 parts of vinylbenzene, 1 part of hydroxyethyl methylacrylate adds in the reactor, stirred 20 minutes, temperature of reaction kettle is heated to 80 ℃, drip initiator, continue to be stirred to emulsion and faint blue light occurs, after 15 minutes, begin to drip good monomer of pre-emulsification (the water high-speed stirring emulsification of remaining monomer and 35 parts 25 minutes) and initiator, in 4 hours pre-emulsion and initiator are all dripped, continue insulation 1 hour, add pH value conditioning agent and regulate pH value to 8.5, cold filtration promptly gets the organic siloxane modified vinylbenzene-acrylate nano emulsion of translucent core/shell structure.

Claims (9)

1. the organic siloxane modified vinylbenzene-acrylate nano emulsion of core/shell structure obtains by hindering emulsion polymerisation process, it is characterized in that vinylbenzene wherein, the monomer component of acrylate are:
1) contain the alkyl acrylate of C1-C10, consumption is the 20-40% of monomer total mass;
2) contain the alkyl methacrylate of C1-C10, consumption is the 20-40% of monomer total mass;
3) contain the hydroxyalkyl methacrylate of C2-C10, consumption is the 2-10% of monomer total mass;
4) contain the thiazolinyl carboxylic acid cross-linking monomer of C3-C6, consumption is the 2-10% of monomer total mass;
5) contain the aromatics of vinyl, consumption is the 10-50% of monomer total mass;
6) contain the polyfunctional group organo-siloxane function monomer of vinyl, consumption is the 1-10% of monomer total mass.
2. the organic siloxane modified vinylbenzene-acrylate nano emulsion of core/shell structure according to claim 1 is characterized in that described alkyl acrylate is one or more mixtures of methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, hexyl acrylate, Isooctyl acrylate monomer.
3. the organic siloxane modified vinylbenzene-acrylate nano emulsion of core/shell structure according to claim 1 is characterized in that described alkyl methacrylate is one or more mixtures of methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, n octyl methacrylate, Isooctyl methacrylate.
4. the organic siloxane modified vinylbenzene-acrylate nano emulsion of core/shell structure according to claim 1 is characterized in that described acrylic acid hydroxy alkyl ester is 2-Hydroxy ethyl acrylate, vinylformic acid-3-hydroxy propyl ester, vinylformic acid-2-hydroxyl butyl ester, vinylformic acid-5-hydroxyl pentyl ester, vinylformic acid-6-hydroxyl one or more mixtures of ester, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-2-hydroxy propyl ester.
5. the organic siloxane modified vinylbenzene-acrylate nano emulsion of core/shell structure according to claim 1 is characterized in that described thiazolinyl carboxylic acid cross-linking monomer is a kind of of vinylformic acid, methacrylic acid or its mixture.
6. the organic siloxane modified vinylbenzene-acrylate nano emulsion of core/shell structure according to claim 1 is characterized in that described vinyl aromatic compounds is one or more mixtures of vinylbenzene, alpha-methyl styrene, 2-chlorostyrene, 3-t-butyl styrene, 3,4-dimethyl styrene.
7. core/shell structure organosilicon-acrylate nano emulsion according to claim 1 is characterized in that described vinyl polyfunctional group organo-siloxane function monomer is one or more mixtures of vinyltrimethoxy silane, vinyl methoxyl group diethoxy silane, vinyltriethoxysilane, vinyl oxyethyl group diisopropoxy silane, vinyl silane triisopropoxide.
8. the preparation method of the organic siloxane modified vinylbenzene-acrylate nano emulsion of the described core/shell structure of claim 1, it is characterized in that comprising the semi-continuous seed emulsion polymerization method that adopts, use extraordinary emulsifying agent, adopt direct initiator or oxidation-reduction initiator, prepare seed micro emulsion emulsion earlier, to adopt hungry charging method in 3-5 hour, to be added drop-wise in the seed microemulsion and react through pre-emulsified monomer again.
9. the preparation method of organosilicon modified styrene according to claim 8-acrylate/nano emulsion is characterized in that comprising the following steps:
(1) preparation seed microemulsion
Water, 10-50% emulsifying agent with 20-50% joins in the reactor earlier, high-speed stirring was disperseed 10-20 minute, add aforesaid propylene acid alkyl ester, the thiazolinyl carboxylic acid of 5-20%, the vinyl aromatic compounds of 50-100% again, be warming up to 75-85 ℃, add the part initiator again, behind the stoichiometric number minute, faint blue light appears in emulsion, restir 5-20 minute, promptly form transparent seed microemulsion.
(2) prepare organic siloxane modified vinylbenzene-acrylate/nano emulsion
Remaining alkyl acrylate, alkyl methacrylate, acrylic acid hydroxy alkyl ester, vinyl aromatic compounds, vinylformic acid cross-linking monomer, vinyl polyfunctional group organosilicon functional monomer, vinyl polyfunctional group organosilicon functional monomer hydrolysis inhibitor, chain-transfer agent, water and emulsifying agent etc. were stirred at a high speed 10-30 minute, make it fully emulsified, obtain monomer pre-emulsion; In 3-5 hour, be added drop-wise in the reactor continuously, react with the seed microemulsion, temperature of reaction maintains 75-85 ℃, reaction finishes, insulation 1-2 hour, cooling, the pH value of regulating microemulsion with pH value conditioning agent, filter discharging, promptly get translucent organosilicon modified styrene-acrylate/nano emulsion; Described chain-transfer agent is alkyl sulfhydryl or the hydrosulphonyl silane of C5-C15, and consumption is the 1-5% of monomer total mass; Described emulsifying agent is response type anion surfactant and nonionogenic tenside, and consumption is at below 3% of monomer total mass, and the first step consumption accounts for the 10-60% of emulsifying agent total mass; Described initiator can be the direct initiator of persulphate, or the oxidation-reduction initiator, and consumption is below 1% of monomer total mass, and the first step consumption accounts for the 20-80% of initiator total mass; Described pH value conditioning agent is carbonate, supercarbonate, phosphoric acid salt, hydrophosphate or the hydrosulfate of basic metal, alkaline-earth metal or ammonium, and consumption is the 0.1-2% of monomer total amount; The monomeric hydrolysis inhibitor of described organosilicon alcoxyl alkoxyl functional is the di-alcohols of C2-C8, and consumption is the 0.1-2% of monomer total mass.
CN 03126653 2003-05-26 2003-05-26 Organic siloxane modified phenylethylene-acrylic ester nano-emulsion and preparing method thereof Pending CN1456577A (en)

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CN1938390B (en) * 2004-03-31 2012-03-21 巴斯福股份公司 Coating masses made from low-emission binding agents
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